Regioselective Arrangement and Bond Activation of the Metallacycles Composed of the Heavier Group 14 Elements

• Project/Area Number: 21750057
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: TANABE Makoto Tokyo Institute of Technology, 資源化学研究所, 助教 (80376962)
• Project Period (FY): 2009 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2010: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2009: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
• Keywords: ケイ素 / メタラサイクル / 不飽和有機分子 / 水素 / 10族遷移金属 / ポリシラン / 高分子合成 / ゲルマニウム / 脱水素カップリング反応 / スズ / 白金 / オリゴゲルマン / 環拡大反応 / アルキン / パラジウム

Research Abstract

This study demonstrates new preparation of metallacycles composed of silicon, germanium, and tin and their chemical properties. A new and convenient synthetic method for oligogermanes was developed via these germametallacycles precursors. Nickel-catalyzed dehydrocoupling precise polymerizations of hydrosilanes produced cyclic oligosilanes with narrow molecular weight distribution.

Research Products

• [Journal Article] Ge-Ge Bond-Forming Reactions from Bis(germyl)palladium Complexes with Chelating Diphosphine Ligands (2011)
  • Author(s): 田邊真, 半沢公也, 小坂田耕太郎
  • Journal Title: Phosphorus, Sulfur, and Silicon and the Related Elements (掲載決定)
• [Journal Article] Synthesis and Characterization of Platinasilsesquioxane Complexes and their Reaction with Arylboronic Acid (2011)
  • Author(s): Neli Mintcheva, 田邊真, 小坂田耕太郎
  • Journal Title: Organometallics 30 Pages: 187-190
  • Peer Reviewed
• [Journal Article] Preparation and Reactivity of an O,O-Chelating Silsesquioxane- Palladium Complex (2011)
  • Author(s): 田邊真, 武藤康二, Neli Mintcheva, 小坂 田耕太郎
  • Journal Title: J.Organomet.Chem. 696 Pages: 1211-1215
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of a Dinuclear Platinum Complex with Silsesquioxanate Ligand (2011)
  • Author(s): Neli Mintcheva, Makoto Tanabe, Kohtaro Osakada, Ivelina Georgieva, Tzvetan Mihailov, Natasha Trendatilova
  • Journal Title: J.Organomet.Chem. Volume: 696 Pages: 1211-1215
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of Platinasilsesquioxane Complexes and their Reaction with Arylboronic Acid (2011)
  • Author(s): Neli Mintcheva, Makoto Tanabe, Kohtaro Osakada
  • Journal Title: Organometallics Volume: 30 Pages: 187-190
  • Peer Reviewed
• [Journal Article] Sila- and Germametallacycles of Late Transition Metals (2010)
  • Author(s): 田邊真, 小坂田耕太郎
  • Journal Title: Organometallics 29 Pages: 4702-4710
  • Peer Reviewed
• [Journal Article] Preparation and Thermal Reaction of Tetrastannapalladacyclopentane. (2010)
  • Author(s): 田邊真, 半沢公也, 小坂田耕太郎
  • Journal Title: Sn-Sn Bond Formation and Cleavage, Organometallics 29 Pages: 3535-3540
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of a Dinuclear Platinum Complex with Silsesquioxanate Ligand,J.Organomet. (2010)
  • Author(s): Neli Mintcheva, 田邊真, 小坂田耕太郎, Ivelina Georgieva, Tzvetan Mihailov, Natasha Trendafilova
  • Journal Title: Chem. 695 Pages: 1738-1743
  • Peer Reviewed
• [Journal Article] Sila- and Germametallacycles of Late Transition Metals (2010)
  • Author(s): Makoto Tanabe Kohtaro Osakada
  • Journal Title: Organometallics Volume: 29 Pages: 4702-4710
  • Peer Reviewed
• [Journal Article] Preparation and Thermal Reaction of Tetrastannapalladacyclopentane. Sn-Sn Bond Formation and Cleavage (2010)
  • Author(s): Makoto Tanabe, Masaya Hanzawa, Kohtaro Osakada
  • Journal Title: Organometallics Volume: 29 Pages: 3535-3540
  • Peer Reviewed
• [Journal Article] Preparation and Reactivity of an O,O-Chelating Silsesquioxane-Palladium Complex (2010)
  • Author(s): Makoto Tanabe, Kohji Mutou, Neli Mintcheva, Kohtaro Osakada
  • Journal Title: J.Organomet.Chem. Volume: 695 Pages: 1738-1743
  • Peer Reviewed
• [Journal Article] Formation and Ring Expansion of Germaplatinacycles via Dehydrogenative Ge-Ge and Ge-Pt Bond-Forming Reactions (2009)
  • Author(s): 田邊真, 半沢公也, 石川尚子, 小坂田耕太郎
  • Journal Title: Organometallics 28 Pages: 6014-6019
  • Peer Reviewed
• [Journal Article] Formation and Ring Expansion of Germaplatinacycles via Dehydrogenative Ge-Ge and Ge-Pt Bond-Forming Reactions (2009)
  • Author(s): Makoto Tanabe, Masaya Hanzawa, Naoko Ishikawa, Kohtaro Osakada
  • Journal Title: Organometallics 28 Pages: 6014-6019
  • Peer Reviewed
• [Journal Article] Planar Tetranuclear and Dumbbell-shaped Octanuclear Pd Complexes with Bridging Silylene Ligands (2009)
  • Author(s): Tetsuyuki Yamada, Akane Mawatari, Makoto Tanabe, Kohtaro Osakada, Tomoaki Tanase
  • Journal Title: Angew.Chem., Int.Ed. 48 Pages: 568-571
  • Peer Reviewed
• [Journal Article] Dialkyl- and diaryl-platinum(II)complexes with secondary phosphines.Preparation, structure and thermal reaction giving the metallopolymer (2009)
  • Author(s): Masaki Kakeya, Makoto Tanabe, Yoshiyuki Nakamura, Kohtaro Osakada
  • Journal Title: J.Organomet.Chem. 694 Pages: 2270-2278
  • Peer Reviewed
• [Journal Article] Ge-Ge Bond-Forming Reactions from Bis(germyl)palladium Complexes with Chelating Diphosphine Ligands
  • Author(s): Makoto Tanabe, Masaya Hanzawa, Kohtaro Osakada
  • Journal Title: Phosphorus, Sulfur, and Silicon and the Related Elements Volume: (In press)
• [Presentation] 後周期金属シルセスキオキサン錯体の合成と反応 (2011)
  • Author(s): Mintechva Neli, 武藤康二, 田邊真, 小坂田耕太郎
  • Organizer: 日本化学会第91春季年会1A3-49
  • Place of Presentation: 神奈川大学
  • Year and Date: 2011-03-26
• [Presentation] 後周期金属シルセスキオキサン錯体の合成と反応 (2011)
  • Author(s): Mintechva Neli, 武藤康二, 田邊真, 小坂田耕太郎
  • Organizer: 日本化学会第91年会春季年会
  • Place of Presentation: 神奈川大学,横浜
  • Year and Date: 2011-03-26
• [Presentation] Planar-hexagonal Pd-Pt tetranuclear complexes (2010)
  • Author(s): 田邊真, 湯本遼平, 山田哲行, 小坂田耕太郎
  • Organizer: Pacifichem 2010
  • Place of Presentation: 米国ホノルル
  • Year and Date: 2010-12-17
• [Presentation] Planar-hexagonal Pd-Pt tetranuclear complexes (2010)
  • Author(s): Makoto Tanabe, Ryouhei Yumoto, Tetsuyuki Yamada Kohtaro Osakada
  • Organizer: Pacifichem 2010
  • Place of Presentation: Honolulu, Hawai
  • Year and Date: 2010-12-17
• [Presentation] Preparation and Structure of Planar Hexagonal Pd-Pt Complexes with Bridging Silylene Ligands (2010)
  • Author(s): Makoto Tanabe, Ryouhei Yumoto, Kohtaro Osakada
  • Organizer: the 3rd Asian Silicon Symposium(ASIS-III 2010)
  • Place of Presentation: 杭州,中国
  • Year and Date: 2010-10-19
• [Presentation] Preparation and Structure of Planar Hexagonal Pd-Pt Complexes with Bridging Silylene Ligands (2010)
  • Author(s): 田邊真, 湯本遼平, 小坂田耕太郎
  • Organizer: the 3rd Asian Silicon Symposium P29
  • Place of Presentation: 中国杭州
  • Year and Date: 2010-10-18
• [Presentation] 14族元素-遷移金属で構成される新構造多核錯体の合成と元素配列変換 (2010)
  • Author(s): 田邊真, 福田智子, 湯本遼平, 千葉舞, 小坂田耕太郎
  • Organizer: 第57回有機金属化学討論会O2-11
  • Place of Presentation: 中央大学
  • Year and Date: 2010-09-17
• [Presentation] 14族元素-遷移金属で構成される新構造多核錯体の合成と元素配列変換 (2010)
  • Author(s): 田邊真, 福田智子, 湯本遼平, 千葉舞, 小坂田耕太郎
  • Organizer: 第57回有機金属化学討論会
  • Place of Presentation: 中央大学,東京
  • Year and Date: 2010-09-17
• [Presentation] Germa- and Stannametallacycles through Dehydrocoupling Reactions of H_2EPh_2 (E = Ge, Sn) Promoted By Group 10 Metal Complexes (2010)
  • Author(s): 田邊真, 半沢公也, 石川尚子, 小坂田耕太郎
  • Organizer: the 13th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead L29
  • Place of Presentation: オーストリア国グラーツ
  • Year and Date: 2010-07-14
• [Presentation] Germa- and Stannametallacycles through Dehydrocoupling Reactions of H_2EPh_2(E=Ge,Sn) Promoted By Group 10 Metal Complexes (2010)
  • Author(s): Makoto Tanabe, Masaya Hanzawa, Naoko Ishikawa, Kohtaro Osakada
  • Organizer: the 13th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL-13)
  • Place of Presentation: Graz, Austria
  • Year and Date: 2010-07-14
• [Presentation] プロトン供与体との反応による平面構造四核パラジウム錯体の骨格変換 (2010)
  • Author(s): 田邊真, 千葉舞, 半沢公也, 小坂田耕太郎
  • Organizer: 日本化学会第91春季年会1B2-20
  • Place of Presentation: 近畿大学
  • Year and Date: 2010-03-26
• [Presentation] プロトン供与体との反応による平面構造四核パラジウム錯体の骨格変換 (2010)
  • Author(s): 田邊真, 千葉舞, 半沢公也, 小坂田耕太郎
  • Organizer: 日本化学会第90年会春季年会
  • Place of Presentation: 近畿大学
  • Year and Date: 2010-03-26
• [Presentation] シリレン配位子が橋架けする平面構造パラジウム四核錯体の反応性 (2009)
  • Author(s): 田邊真, 福田智子, 馬渡あかね, 小坂田耕太郎
  • Organizer: 第13回ケイ素化学協会シンポジウムP06
  • Place of Presentation: 唐津
  • Year and Date: 2009-10-30
• [Presentation] シリレン配位子が橋架けする平面構造パラジウム四核錯体の反応性 (2009)
  • Author(s): 田邊真, 福田智子, 馬渡あかね, 小坂田耕太郎
  • Organizer: 第13回ケイ素化学協会シンポジウム
  • Place of Presentation: 佐賀県 唐津
  • Year and Date: 2009-10-30
• [Presentation] 10族金属ゲルマサイクルを基軸とするオリゴゲルマンの新規合成法 (2009)
  • Author(s): 半沢正也, 田邊真, 小坂田耕太郎
  • Organizer: 第13回ケイ素化学協会シンポジウム
  • Place of Presentation: 佐賀県 唐津
  • Year and Date: 2009-10-30
• [Presentation] 含金属ゲルマサイクルを鍵とする平面構造パラジウム四核錯体の合成と可逆的な構造変換 (2009)
  • Author(s): 半沢公也, 石川尚子, 田邊真, 小坂田耕太郎
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2009-09-25
• [Presentation] 平面構造パラジウム四核錯体への金属フラグメントの付加と動的挙動 (2009)
  • Author(s): 福田智子, 田邊真, 小坂田耕太郎
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2009-09-25
• [Presentation] 11族金属錯体が付加する平面構造パラジウム四核錯体の構造と動的挙動 (2009)
  • Author(s): 田邊真, 福田智子, 星野剛, 山田哲行, 小坂田耕太郎
  • Organizer: 第56回有機金属討論会P2A-28
  • Place of Presentation: 同志社大学
  • Year and Date: 2009-09-10
• [Presentation] 11族金属錯体が付加する平面構造パラジウム四核錯体の構造と動的挙動 (2009)
  • Author(s): 田邊真, 福田智子, 星剛, 山田哲行, 小坂田耕太郎
  • Organizer: 第56回有機金属討論会
  • Place of Presentation: 同志社大学
  • Year and Date: 2009-09-10
• [Presentation] Formation and Dynamic Behaviour of the Pentanuclear Complexes by Addition of CuI and AgI on the Planar Pd_4Si_3 or Pd_4Ge_3 Cores (2009)
  • Author(s): 田邊真, 福田智子, 星野剛, 山田哲行, 小坂田耕太郎
  • Organizer: XVIII EuCheMS Conference on Organometallic Chemistry
  • Place of Presentation: スゥエーデン ヨーテボリ
  • Year and Date: 2009-06-24
• [Presentation] Formation and Dynamic Behaviour of the Pentanuclear Complexes by Addition of Cul and Agl on the Planar Pd_4Si_3 or Pd_4Ge_3 Cores (2009)
  • Author(s): 田邊真, 福田智子, 星剛, 山田哲行, 小坂田耕太郎
  • Organizer: XVIII EuCheMS Conference on Organometallic Chemistry
  • Place of Presentation: Goteborg, Sweden
  • Year and Date: 2009-06-24
• [Presentation] 14族元素配位子をもつ平面構造パラジウム多核錯体の合成 (2009)
  • Author(s): 田邊真
  • Organizer: 文部科学省科学研究費補助金特定領域研究「元素相乗系化合物の化学」第5回若手コロキウム
  • Place of Presentation: 群馬県 高崎
  • Year and Date: 2009-04-16